The present invention relates to compositions containing low-foaming nonionic wetting agents.
Due to the varied nature of different compositions, different wetting agents are better suited for some applications while being less suited or totally unsuitable for other applications. While some wetting agents provide the desired properties, such as dispersion or suspension of other ingredients, they are high foaming or not readily biodegradable. Conversely, a wetting agent may be suitably low foaming, but provide less that suitable dispersion or suspension of other ingredients.
Accordingly, the need remains for new wetting agents which are suitable for use in a variety of compositions and applications that can provide improve dissolution, improved rates of mixing with water, improved streaking and filming performance, good wetting, adequate dispersion and/or suspension, suds control and good biodegradability, while avoiding incompatibility with other components of the compositions.
In accordance with a first aspect of the present invention, a composition comprising an ether-capped poly(oxyalkylated) alcohol wetting agent is provided. The composition comprises:
(a) from about 0.01% to about 50%, preferably from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, by weight of the composition of a wetting agent, wherein said wetting agent comprises an ether-capped poly(oxyalkylated) alcohol having the formula:
RO(R1O)xCH(CH3)OR2
wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R1 may be the same or different, and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of:
(i) a 4 to 8 membered substituted, or unsubstituted heterocyclic ring containing from 1 to 3 hetero atoms; and
(ii) linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms;
provided that when R2 is (ii) then either at least one of R1 is other than C2 to C3 alkylene or R2 has from 6 to 30 carbon atoms; and
(b) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
Once again, the first aspect of the present invention is directed toward compositions comprising low-foaming nonionic wetting agents. The wetting agents of the present invention are of the formula:
RO(R1O)xCH(CH3)OR2
In one aspect of the present invention, R is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radical having from about 1 to about 20 carbon atoms. Even more preferably R is a linear or branched, saturated, aliphatic hydrocarbon radical having from about 4 to about 18, preferably from about 8 to about 16, carbon atoms.
In one aspect of the present invention R, R1 and R2 are selected such that the ether-capped poly(oxyalkylated) alcohol contains one or more chiral carbon atoms.
In one aspect of the present invention the ether-capped poly(oxyalkylated) alcohol is a mixture of ether-capped poly(oxyalkylated) alcohols. This mixture can be obtained in a variety of ways, for example, by mixing two ether-capped poly(oxyalkylated) alcohols together, or by forming the ether-capped poly(oxyalkylated) alcohols from a mixture of alcohols, in which the reaction used to produce the ether-capped poly(oxyalkylated) alcohols forms a racemic mixture, or by alkoxylating under conditions such that the ether-capped poly(oxyalkylated) alcohol produced is a mixture with a range of different alkoxy groups present on each ether-capped poly(oxyalkylated) alcohol. These example are intended to be illustrative, and in no way limiting in the scope of the invention.
In one aspect of the present invention, R is a hydrocarbon radical of the formula: 
wherein R4, R5, and R6 are each independently selected from hydrogen and C1-C3 alkyl, more preferably hydrogen and C1-C2 alkyl, even more preferably hydrogen and methyl, provided that R4, R5, and R6 are not all hydrogen and, when t is 0, at least R4 or R5 is not hydrogen; q, r, s, and t are each independently integers from 0 to 13. In one more preferred form of this aspect R is selected from the formulas: 
wherein n, m, j and k are each independently integers from 0 to 13.
In one aspect of the present invention R2 is a hydrocarbon radical of the formula:
xe2x80x94C(CH3)2R3
wherein R3 is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30, more preferably 1 to 20, even more preferably 1 to 15, carbon atoms. In one embodiment of this aspect of the present invention, R3 is xe2x80x94CH2CH3.
In the novel compounds of the present invention, when R2 is (ii) then either at least one of R1 is other than C2 to C3 alkylene or R2 has from 6 to 30 carbon atoms. That is, when R2 is (ii) R2 is either a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 6 to about 30 carbon atoms or a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 1 to about 30 carbon atoms, with at least one of R1 being other than C2 to C3 alkylene. For example, when R2 is a hydrocarbon of the formula:
xe2x80x94(CH2)yxe2x80x94X
where y and X are described hereafter, or R2 is a hydrocarbon radical of the formula:
C(CH3)2R3
where R3 is hereinbefore described, then at least one of R1 is other than C2 to C3 alkylene. For example, if x is 5, and R2 is (CH2)yxe2x80x94X, then the ether-capped poly(oxyalkylated) alcohol could have the formula:
RO(CH2CH(CH2CH3)O)5CH(CH3)Oxe2x80x94(CH2)yxe2x80x94X
or
RO(CH2CH2O)4(CH2CH(CH2CH3)O)CH(CH3)Oxe2x80x94(CH2)yxe2x80x94X
or
RO(CH2CHCH3O)(CH2CH(CH2CH3)O)4CH(CH3)Oxe2x80x94(CH2)yxe2x80x94X
Similarly, for example if R2 is xe2x80x94C(CH3)2R3 and x is 7, then the ether-capped poly(oxyalkylated) alcohol could have the formula:
RO(CH2CH2O)6(CH2CH2(CH2CH3)O)CH(CH3)Oxe2x80x94C(CH3)2R3
or
RO(CH2CHCH3O)4(CH2CH(CH2CH3)O)3CH(CH3)Oxe2x80x94C(CH3)2R3
or
RO(CH2CH2O)3(CH2CHCH3O)2(CH2CH(CH2CH3)O)(CH2CH(CH2CH2CH3CH)O)CH(CH3)Oxe2x80x94C(CH3)2R3
These above examples are included merely for illustrative purposes and are not to be construed in any manner as limiting of the scope of the present invention.
In one aspect of the present invention R2 is a 4 to 8 membered substituted or unsubstituted heterocyclic ring containing from 1 to 3 heteroatoms. In one embodiment of this aspect of the invention the heteroatoms are selected from the group comprising oxygen, nitrogen, sulfur and mixtures thereof. In one embodiment of this aspect of the invention R2 is a 5 or 6 member heterocycle. In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: 
wherein each R7 is independently selected from the group consisting of hydrogen and linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon or alkoxy radicals having from about 1 to about 10 carbon atoms, or R7 is a saturated or unsaturated, substituted or unsubstituted, alicyclic or aromatic hydrocarbon radical having from about 1 to about 10 carbon atoms, which is fused to the heterocyclic ring; each A is independently selected from the group consisting of O, and N(R8)a, wherein R8 is independently selected from the group consisting of hydrogen and linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radicals having from about 1 to about 10 carbon atoms, and a is either 0 or 1; and z is an integer from 1 to 3.
In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: 
wherein R7 is defined as above. Preferably, the above ether-capped poly(oxyalkylated) alcohol contains a chiral center.
In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: 
wherein R7 and R8 are defined as above.
In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: 
In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: 
In one aspect of the present invention R2 is a 7 to 13 membered substituted, or unsubstituted polycyclic ring. In one embodiment of this aspect of the present invention R2 is selected from the group consisting of substituted or unsubstituted adamantane, substituted or unsubstituted norbornane, substituted or unsubstituted nortricyclene, and substituted or unsubstituted bicyclo[2.2.2]octane. In another embodiment of this aspect of the present invention R2 is a substituted or unsubstituted adamantane.
In one embodiment of the invention, R is selected from the group consisting of linear or branched, aliphatic hydrocarbon radicals having from about 7 to about 11 carbon atoms; x is a number from 6 to about 10; and R2 is selected from the group consisting of a hydrocarbon radical of the formula:
xe2x80x94C(CH3)2R3
wherein R3 is selected from the group consisting of linear or branched, aliphatic radicals having from about 2 to about 5 carbon atoms.
In one aspect of the present invention R2 is a hydrocarbon of the formula:
xe2x80x94(CH2)yxe2x80x94X
wherein y is an integer from 0 to 7, X is a 4 to 8, preferably 5 or 6, membered substituted or unsubstituted, saturated or unsaturated, cyclic or aromatic hydrocarbon radical. In another embodiment of this aspect of the present invention y is an integer from 1 to 2, and X is selected from the group consisting of 5 to 8 membered substituted or unsubstituted, aromatic hydrocarbon radicals.
In another embodiment of this aspect of the present invention y is 0 and X is a 5 or 6 membered substituted or unsubstituted, saturated or unsaturated, cyclic or aromatic hydrocarbon radical.
In another embodiment of this aspect of the present invention X is selected from the group consisting of: 
wherein each R9 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon or alkoxy radicals having from about 1 to about 10 carbon atoms, or each R9 is a saturated or unsaturated, substituted or unsubstituted, alicyclic or aromatic hydrocarbon radical having from about 1 to about 10 carbon atoms, which is fused to the ring; and w is an integer from 1 to 3.
In another embodiment of this aspect of the present invention X is selected from the group consisting of: 
wherein each R9 is defined as above.
In another embodiment of this aspect of the present invention X is selected from the group consisting of: 
In one aspect of the present invention R2 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radical having from about 1 to about 30 carbon atoms, more preferably R2 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radical having from about 1 to about 20 carbon atoms, even more preferably R2 is a linear or branched, saturated, aliphatic hydrocarbon radicals having from about 4 to about 18, preferably from about 8 to about 16, carbon atoms.
In one aspect of the present invention, when x is greater than 2, R1 may be the same or different. That is, R1 may vary between any of the C2 to C7 alkylene units as described above. For instance, if x is 3, R1 may be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, multiple (EO) units and a much smaller number of (PO) units. Similarly, ethylene, and propylene are chosen for example only and the variation may be much larger with selection of linear or branched butylene, pentylene, hexylene and/or heptylene. Preferably, x is from about 2 to about 20, and each R1 is ethylene or propylene. More preferably, x is from about 4 to about 12, and each R1 is ethylene.
The ether-capped poly(oxyalkylated) alcohols used in the compositions of the present invention can be prepared via a variety of different processes. In one aspect of the present invention, the ether-capped poly(oxyalkylated) alcohol may be prepared by the following steps: (a) providing a vinyl ether of the formula:
R2OCHxe2x95x90CH2
wherein R2 is as defined above; (b) providing an alkoxylated alcohol of the formula
RO(R1O)xH
wherein R, R1, and x, are as defined above; and (c) reacting the vinyl ether and alkoxylated alcohol in the presence of a catalyst to form the ether-capped poly(oxyalkylated) alcohol.
In one embodiment of this aspect of the present invention the step of reacting of vinyl ether with alkoxylated alcohol is conducted in the presence of a catalyst. Suitable catalysts include Lewis acids; acids and their salts, both organic and inorganic; pyridinium salts; polymers; clays, such as Spanish sepiolite clay, GIRDLER K-10; aluminosilicates or zeolites, such as HZS-360 zeolite, Hxe2x80x94Y zeolite; activated carbon, such as sulfonated charcoal; transition metal complexes, such as molybedenyl(VI) acetylacetone; transition metal salts, such as lanthum trichloride, ceric ammonium nitrate; 2,3-dichloro-5,6,dicyano-p-benzoquinone; bis(trimethysilyl)sulfate; and mixtures thereof.
Suitable Lewis acids include, but are not limited to, TiCl4, Ti(OiPr)4, ZnCl2, SnCl2, AlCl3, platinum dichloride, copper(II) chloride, phosphorous pentachloride, phosphorous trichloride, cobalt(II) chloride, zinc oxide, iron(II) chloride and BF3-OEt2.
Suitable inorganic acids and salts include mineral acids, such as, phosphoric acid, sulfuric acid, hydrochloric acid, phosphorous oxychloride, aluminium phosphate and ammonium chloride. Furthermore, the mineral acids or their salts can optionally be adsorbed onto a substrate, such as silica gel, or alumina. For example sulfuric acid can be adsorbed on silica gel, or alumina impregnated with zinc chloride.
Suitable organic acids include: carboxylic acids, such as acetic acid, oxalic acid, glycolic acid, citric acid, tartaric acid, maleic acid and oxydisuccinic acid; halogenated carboxylic acids, such as trifluoroacetic acid, heptafluorobutyric acid, dichloroacetic acid, and trichloroacetic acid; and sulfonic and sulfinic acids and their salts such as p-toluenesulfonic acid, p-toluenesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 4-bromobenzenesulfonic acid, naphthalenesulfonic acid, (xc2x1)-10-camphorsulfonic acids, xylenesulfonic acid, cumenesulfonic acid, and alkylbenzene sulfonic acid.
Suitable pyridinium salts include, but are not limited to, pyridinium p-toluenesulfonate (PPTS), pyridinium p-toluenesulfinate, pyridinium hydrochloride, pyridinium hydrobromide, pyridinium hydrogen bisulfate, pyridinium hydrogen sulfate and mixtures thereof.
Suitable transition metal complexes include, but are not limited to, molybedenyl(VI) acetylacetone; transition metal salts, such as lanthum trichloride, ceric ammonium nitrate; 2,3-dichloro-5,6,dicyano-p-benzoquinone, mercury(II) acetate, mercury(II) trifluroacetate, copper(II) acetylacetonate and tetracarbonylbis(cyclopentadienyl)diiron.
Suitable polymers include, but are not limited to, polymeric ion exchange resins, or polyvinyl pyridines. Suitable polymeric ion exchange resins include those of the Amberylst series, such as AMBERYLST(copyright)15, available from Rohm and Haas, the DOWEX(copyright) series, such as DOWEX 50X8-50 avaliable from Dow; REILLEX 424, available from Reilly Industries; the Amberlite series, such as AMBERLITE IRA-400, or AMBERLITE IR-118, available from Rohm and Haas; the ENVIROCAT series, such as ENVIROCAT EPZG, available from Contract Chemicals; and combinations thereof. Suitable polyvinyl pyridines can be unsubstituted or substituted, such as substituted on the vinyl group and/or on the pyridine ring. Examples of suitable polyvinyl pyridines include, but are not limited to, poly(4-vinylpyridine trifluoromethanesulfonate), poly(2-vinylpyridine trifluoromethanesulfonate), poly(4-vinylpyridine p-toluenesulfonate), poly(2-vinylpyridine p-toluenesulfonate), poly(4-vinylpyridine chloride), poly(2-vinylpyridine chloride), poly(4-vinylpyridine bromide), poly(2-vinylpyridine bromide), and mixtures thereof. These polymeric catalysts have the additional advantage of being easy to separate from the surfactant produced.
Other suitable catalysts include bis(trimethysilyl)sulfate, iodotrimethylsilane, allytrimethyl silane, hexamethyldisilane, iodine, bromine, iron(II) sulfate, triphenylphosphine, aluminium sulfate, alkylether sulfuric acids, alkyl sulfuric acids, lithium perchlorate, lithium tetrafluoroborate, acetonyltriphenylphosphonium bromide, zirconium hydroxide, potassium cyanide, and platinum oxide.
Preferred catalysts include the sulfonic acids, Lewis acids, polyvinyl pyridines, methanesulfonic acid, AMBERYLST(copyright)15, acidic versions of DOWEX(copyright) and pyridinium p-toluenesulfonate (PPTS), with polyvinyl pyridines, pyridinium p-toluenesulfonate (PPTS), p-toluenesulfonic acid, DOWEX(copyright), AMBERYLST(copyright)15 and methanesulfonic acid being the most preferred.
Mixtures of catalysts are also within the scope of the present invention. Similarly, the uses of supported, such as in a column for a continuous reaction, and unsupported catalysts are also within the scope of the present invention.
The catalysts are preferably employed at amounts of about 0.005 mol % to about 20.0 mol %, more preferably from about 0.01 mol % to about 10.0 mol %, even more preferably from about 0.01 mol % to about 5.0 mol %, even more preferably still from about 0.01 mol % to about 2.0 mol %, even more preferably still from about 0.01 mol % to about 1.5 mol %, based on the number of moles of alkoxylated alcohol in step (c) of the process. Other suitable catalysts can be found in U.S. Pat. No. 4,272,394, and in PCT publications, WO 94/22800, WO 93/04153, WO96/00253 and WO 98/17379, all of which are incorporated herein by reference.
In one embodiment of this aspect of the present invention the reaction is conducted in the presence of a solvent, or mixtures of solvents. It is preferred that the solvent be a polar aprotic solvent. Suitable solvents include, but are not limited to, hexane, benzene, toluene, xylene, mesitylene, dichloromethane, tetrahydrofuran, dioxane, diethylether, methyl tert-butylether, acetone, acrylonitrile, or the like. Furthermore, the reaction is preferably conducted at temperatures ranging from about xe2x88x9220xc2x0 C. to about 300xc2x0 C., more preferably from about xe2x88x9210xc2x0 C. to about 250xc2x0 C., and most preferably from about 10xc2x0 C. to about 60xc2x0 C. Lastly, the reaction is preferably conducted at pressures ranging from about 0.5 atmospheres to about 100 atmospheres, and more preferably from about 0.8 atmospheres to about 10 atmospheres.
In another embodiment of this aspect of the present invention the step of reacting vinyl ether with alkoxylated alcohol is conducted in the absence of a solvent.
Further disclosure on suitable solvents and catalysts can be found in xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, by Jerry March, 4th ed., Wiley-Interscience, 1992, xe2x80x9cComprehensive Organic Transformationsxe2x80x9d by Richard C. Larock, VCH Publishers, 1989, and xe2x80x9cProtective Groups in Organic Synthesisxe2x80x9d 3RD ed. by Theodora W. Greene and Peter G. M. Wuts, Wiley-Interscience, 1999 the relevant portions of which are incorporated herein by reference.
In one embodiment of the present invention, the process is performed as a batch process. That is, the reaction is let to proceed to completion, or near completion, and then final product is removed. In another embodiment of the present invention, the process is performed as a continuous process. That is, the product of the process is continuously removed from the reaction vessel while starting material is added at a comparable rate.
In one embodiment of the present invention the vinyl ether is reacted with the alkoxylated alcohol at a mole ratio of from about 5:1 to about 0.5: 1, more preferably from about 3:1 to about 0.75:1, more preferably still from about 1.5:1 to about 0.9:1.
In one embodiment of the process of the present invention the process may be conducted in an inert gas. This may be done by sparging with any suitable inert gas, such as nitrogen, helium, neon, argon or the like.
In one embodiment of the present invention reaction step (c) above may be followed by optional step (d). Step (d) is a step in which the reaction step (c) is quenched, preferably by the addition of base. The amount of the ether capped poly(oxyalkylated) alcohol present in the reaction mixture will depend upon many factors, including but not limited to, starting materials, temperature, catalyst selection and the like. Quenching stops the reaction of the starting materials, and ensures that any ether capped poly(oxyalkylated) alcohol produced does not undergo further reaction or revert back to the starting materials. The quenching of step (c) produces a mixture which contains ether capped poly(oxyalkylated) alcohol, as well as unreacted starting materials, catalyst and the products of any side reactions. In one embodiment of this present invention, the quenching of the reaction of step (c) is done when the reaction mixture preferably contains at least 90%, more preferably at least 95% by weight of ether capped poly(oxyalkylated) alcohol. The remaining portion of the mixture, up to 10%, more preferably up to 5% by weight, comprises unreacted starting material as well as products of side reactions, such as byproduct acetals. In one aspect of this embodiment of the present invention the base may be optionally selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, alkali metal alcoholates, alkanolamines, alkylamines, aromatic amines and mixtures thereof. In a further aspect of the present invention the base may be optionally selected from the group consisting of potassium carbonate, sodium carbonate, sodium bicarbonate, sodium methoxylate, sodium ethoxylate, potassium tert-butyloxylate, triethylamine, triethanolamine and mixtures thereof. In another aspect of this embodiment of the present invention, the base may be in the form of an aqueous solution. In a further aspect of this embodiment of the present invention, the aqueous solution may be at a temperature of from about 20xc2x0 C. to about 60xc2x0 C.
The expression xe2x80x9cproduct of step (c)xe2x80x9d is meant to include not only the ether-capped poly(oxyalkylated) alcohol but also any unreacted starting materials or any materials produced from side reactions, such as dimers, which would be present at the conclusion of step (c).
In one embodiment of the present invention the process of the present invention may optionally further comprise a step (e). Step (e) is removal of color bodies and/or odors from the product of steps (c) or (d). In one aspect of this embodiment of the present invention removal of the color bodies and/or odors is obtained by contacting the product of steps (c) or (d) with a reagent. The reagent can either be an oxidant, or a reductant. Suitable oxidants include hydrogen peroxide. Suitable reductants include sodium borohydride, and hydrogen over a palladium/carbon catalyst. In a further aspect of this embodiment of the present invention the color bodies and/or odors are removed by contacting the product of step (c) first with an oxidant and then a reductant, or first with a reductant and then an oxidant. The color bodies may also be removed by treating the product mixture with a activated charcoal (carbon).
In one embodiment of the present invention the ether-capped poly(oxyalkylated) alcohol produced in steps (c) or (d) may optionally be removed from the product of steps (c) or (d) by centrifuging.
Some representative examples of this possible synthetic route of this aspect of the invention are demonstrated via the following diagrams. 
The ether-capped poly(oxyalkylated) alcohol product is then collected by means common in the art such as extraction. If so desired, stripping, distillation or various other means may be used to treat the ether-capped poly(oxyalkylated) alcohol product before use. The ether-capped poly(oxyalkylated) alcohols made by the process disclosed herein may contain related impurities, which will not adversely affect performance.
Compositions and Methods
The ether-capped poly(oxyalkylated) alcohol wetting agents of the present invention may be used in a variety of applications, such as antifoaming agents, in drilling muds, etc., in a wide range of fields, such as in biocides, meat cleaning, foods, pharmaceuticals, polymer latexes, etc. The ether-capped poly(oxyalkylated) alcohol wetting agents have the properties of good biodegradability, low-sudsing as well as cleaning which allows them to be used in a wide range of diverse and radically different applications. For any particular application which desires a specific physical property, such as HLB or cloud point, an ether-capped poly(oxyalkylated) alcohol surfactant, or mixtures of ether-capped poly(oxyalkylated) alcohol surfactant, may be used. The desired propertied are obtained varying the selection of R, R1, x and R2 for any ether-capped poly(oxyalkylated) alcohol surfactant or mixtures of these surfactants. Further examples of possible application for these surfactants can be found in xe2x80x9cNonionic Surfactantsxe2x80x9d edited by Martin J. Schinck, Surfactant Science Series, Marcel Dekker, NY, Volume 1; xe2x80x9cNonionic Surfactants: Physical Chemistryxe2x80x9d edited by Martin J. Schinck, Surfactant Science Series, Marcel Dekker, NY, Volume 23; xe2x80x9cNonionic Surfactants: Polyoxyalkylene Block Copolymersxe2x80x9d edited by Vaughn M. Nace, Surfactant Science Series, Marcel Dekker, NY, Volume 60; and L. G. Lundsted and I. R. Schmolka, in xe2x80x9cBlock and Graft Copolymerizationxe2x80x9d, Vol. 2 (R. J. Ceresa, ed.), John Wiley and Sons, Ltd., London, 1976, pp. 113-272, incorporated herein by reference.
The compositions of the present invention contain an adjunct ingredient. In general, an adjunct is any material required to transform a composition containing only the minimum essential ingredients into a composition useful for the desired end use, such as a fungicidal compound for a fungicide, a dentifrice for a toothpaste, sand for cement, etc. In preferred embodiments, adjuncts are easily recognizable to those of skill in the art as being absolutely characteristic of products, especially of products intended for direct use by a consumer in a domestic environment.
The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which the composition is to be used. The selection of the adjunct will depend upon the type and use of the composition. Non-limiting illustrative examples of compositions including the wetting agents of the present invention as well as suitable adjunct(s) for the illustrative compositions are described hereinafter.
Similarly, the wetting agents of the present invention may also be used in a variety of different methods, with or without any adjunct ingredients. For example, a method of treating waste water from a paper pulp plant involves the addition of one or more of the novel wetting agents of the present invention to improve the treatment of the waste water.
Use levels of the overall compositions can vary widely depending on the intended application, ranging for example from a few ppm in solution to use of the neat composition. Typically, levels of adjuncts are from about 0.00001% to about 99.9%, by weight of the compositions.
Some illustrative compositions of the present invention include:
1. Polymers
The compositions of the present invention may be polymer compositions. That is they may be, for example, polymeric latexes, containing the wetting agent of the present invention as well as monomer and other adjuncts conventionally present. The wetting agents may be present during polymerization to improve the process. For example, a wetting agent could be present in a solution or suspension of monomer to improve the distribution of the monomer in solution and hence increase the rate of polymerization. Alternatively, the wetting aid could be present to affect in some manner the physical properties of the polymer or the polymer composition. The wetting agent may also be used to allow for even distribution, polymerization and/or drying on a surface to which a polymeric dispersion is applied. For example the wetting agents of the present invention could be used to aid in the dispersal of polymeric carpet backing, see WO 99/52968 filed Apr. 14, 1998, or to emulsify polymeric compositions which are applied to fabrics, see U.S. Pat. No. 4,088,592. Another example is that the wetting agent of the present invention may be used in the production of, and present in polymeric films and laminates, especially films for stretch wrapping. See U.S. Pat. No. 4,066,811, Naito et al, granted Jan. 3, 1978. See also Daeumer et al., issued Sep. 20, 1994.
In such polymeric compositions common adjutants include, but are not limited to, monomers, fillers, solvent, flame retardant, cross-linking agents, preservatives, pigments, catalysts, co-catalysts, anti-foaming agents, resins, viscosity control agents, wetting agents other than those of the present invention, polymers, initiators, chain transfer agents, anti-oxidants, UV absorbers and mixtures thereof.
2. Anti-Foaming/Suds Suppressors
The wetting agents of the present invention may be used as partial or total replacements for convention anti-foaming compositions. At present most, if not all, commercial anti-foaming compositions are based around one or more silicon containing compounds. While these provide adequate anti-foaming, they are expensive and typically a complex mixture of silicon containing compounds as well as other ingredients. The wetting agents of the present invention have none of these disadvantages associated with conventional anti-foams. Furthermore, the wetting agents of the present invention have the added advantage of being readily biodegradable.
The wetting agents of the present invention may be used as foam control additives in a variety of applications, such as food, agriculture, and paper. They also carry the added advantage of being able to control foaming while also acting as a wetting agent. This dual advantage of these wetting agents allows for them to replace two components in a composition with a single one that provide both the properties desired. Similarly, the wetting agents of the present invention may be used in a method for reducing or controlling the foaming of a composition by adding a foam reducing/controlling amount of a wetting agent of the present invention. Further information on foam control compositions and their applications can be found in U.S. Pat. No. 5,990,181 to Spyropoulos et. al., issued Nov. 23, 1999 and U.S. Pat. No. 5,843,734 to Shonaka et. al., issued Dec. 1, 1998; and WO 98/00216 to Rhone-Poulenc, published Jan. 8, 1998, and WO 98/30305 to Henkel Corporation, published Jul. 16, 1998.
3. Biocidal Compositions
The wetting agents of the present invention may also be used in biocidal compositions. Biocidal compositions are compositions that have some desired effect on a biological system or organism, such as killing the organism, preventing its reproduction etc. They can be targeted at one specific organism, such as termites, or be designed to act on a wide range of organisms, such as an insecticide. Typically the biocidal compositions contain a biocide or biocides that provide the desired effect on the biological system or organism. Some illustrative example of some biocidal compositions include, but are not limited to, insecticides, miticides, aphicides, fungicides, bacteriocides, molluscicides, acaricides, nematicides, fugicides, plant growth regulators, defoliants, gametocides, herbicides, algicides, viricides, dessicants, insect repellents and the like.
The wetting agents of the present invention may be used in the biocidal composition in many ways. They may, for example, be used to improve delivery of the biocide onto the target organism, improve the dispersion in the composition of the biocide before delivery, and/or improve the suspension of the biocide in a concentrate formula, which is diluted when used.
The wetting agents of the present invention can be used in biocidal compositions of any form, that is, powder, dusts, granules, liquids, emulsions, suspensions, etc.
In such compositions adjutants include, but are not limited to, fillers, solvent, preservatives, pigments, anti-foaming agents, resins, viscosity control agents, wetting agents other than those of the present invention, polymers, diluents, anti-oxidants, UV absorbers, buffering agents, sticking agents, carriers, biocides, and mixtures thereof.
Suitable biocides include, but are no limited to, insecticides, such as organophosphorus compounds disclosed in U.S. Pat. No. 3,244,586, O,O-diethyl O-(3,5,6-trichloropyridine-2-yl) phosphorothioate, also known as chlorpyrifos, see WO 99/33340 published Jul. 8, 1999 and WO 99/29171 published Jun. 17, 1999; miticides; aphicides; fungicides, such as zinc ethylenebis(dithiocarbamate), nickel dimethyldithiocarbamate, and methyl-l(butylcarbamoyl)-2-benzimidazolecarbamate, see WO 99/29171 published Jun. 17, 1999; molluscicides; bacteriocides; acaricides, nematicides; plant growth regulators, such as N-methoxycarbonyl-Nxe2x80x2-4-methgylphenylcarbamoylethylisourea, sodium napthaleneacetate, triazine herbacieds, such as 2-methylthio-4,6-bisethylamino-1,3,5,-triazine, diphenylether herbicides such as 2,4-dichlorophenyl-4xe2x80x2-nitrophenylether, urea herbicides, carbamate herbicides, thiolcarbamate herbicides, pryrdinium herbicides, analine herbicides, pyrazole herbicides and the like, see WO 99/29171 published Jun. 17, 1999; defoliants, such as agent orange; gametocides; herbicides, such as acetochlor, alachlor, metolachlor, aminotriazole, asulam, bentazon, bialaphos, paraquat, bromacil, clethodium, sethoxydim, dicamba, diflufenican, pendimethalin, acifluorfen, fosamine, flupoxam, bromoxynil, imazaquin, norflurazon, 2,4-D, 2,4,5-T, diclofop, fluometuron, chlorimuron, triallate, atrazine, salts of N-phosphonomethylglycine (these are also know as the glyphosates, such as in the herbicidal compositions ROUNDUP(copyright) and ACCORD(copyright) both available from Monsanto, and TOUCHDOWN(copyright) available from Zeneca), and monoisopropylamine salts of N-phosphonomethylglycine. Other suitable herbicides may be found in U.S. Pat. No. 6,093,680, Gillespie et al., issued Jul. 25, 2000, and U.S. Pat. No. 4,933,002, Petroff et al., issued Jun. 12, 1990 and in WO 99/33340 published Jul. 8, 1999; algicides; viricides; insect repellents, such as 2-ethyl-1,3-hexanediol, N-octyl bicycloheptene dicarboxamide, N,N-diethyl-M-toluamide, 2,3,4,5-bis(2-butylene)tetrahydro-2furaldehyde; Di-n-propyl isocinchomeronate, 2-hydroxyethyl-n-octyl sulfide, see WO 99/33340 published Jul. 8, 1999; and mixtures thereof.
The amount of biocide present as well as other ingredients will depend upon not only the target biological system or organism, but also on the location of the organism as well as the means for delivery of the biocidal composition.
Additional information on biocides, biocidal compositions as well as their formulation and delivery can be found in U.S. Pat. No. 4,565,162 Itho et al, issued Apr. 7, 1987; U.S. Pat. No. 4,933,002 Petroff et al., issued Jun. 12, 1990; U.S. Pat. No. 5,332,714 Albrecht et al., issued Jul. 26, 1994; U.S. Pat. No. 5,389,300 Schmitt et al., issued Feb. 14, 1995; U.S. Pat. No. 5,580,840 Harms et al., issued Dec. 3, 1996; U.S. Pat. No. 5,874,096 Hazen issued Feb. 23, 1999; U.S. Pat. No. 5,968,872 Policello et al., issued Oct. 19, 1999; U.S. Pat. No. 6,051,730 Pallas et al issued Apr. 18, 2000; and U.S. Pat. No. 6,093,680 Gillespie et al., issued Jul. 25, 2000; and WO applications 98/17108 published Apr. 30, 1998; 99/29171 published Jun. 17, 1999; 99/33340 published Jul. 8, 1999; and 99/40784 published Aug. 19, 1999.
4. Cements
The wetting agents of the present invention may be used in cement admixtures. The wetting agents may be, for example, present to suspend or disperse ingredients present in the composition, or they may be present to affect the drying rate of the cement or affect the physical properties of the final cement product in some fashion, such as inhibiting shrinkage on drying, or affecting the distribution, size and shape of air entrapped in concrete or mortar. The term cements is intended to cover all similar materials, whether predominately organic or inorganic, such as concrete, mortars, hydraulic cements, and the like. The wetting agents of the present invention are suitable for use in both inorganic cements, such as Portland cement, and in predominately organic cements, such as the styrene/butadiene latex of U.S. Pat. No. 5,300,542 Gopalkrishan issued Apr. 5, 1994.
Typical adjunct ingredients found in cement include, but are not limited to, aggregate, sand, water, shrinkage inhibitors, hardening accelerants, fluid loss control agents, retardants, light weight additives, heavy weight additives, binders, defoamers, solvent, wetting agents other than the wetting agents of the present invention, dyes, pigments, fillers, fluidizing agents, corrosion inhibitors, air entraining agents, polymers, and mixtures thereof. See U.S. Pat. No. 5,779,788 Berke et al., issued Jul. 14, 1998, U.S. Pat. No. 5,085,708 Myoria et al., issued Feb. 4, 1992, U.S. Pat. No. 5,207,831 Cowan issued May 4, 1993, U.S. Pat. No. 5,348,993 Daeumer et al., issued Sep. 20, 1994, and U.S. Pat. No. 5,300,542 Gopalkrishan issued Apr, 5, 1994, U.S. Pat. No. 5,922,796 Colombet et al, issued Jul. 3, 1999 and WO99/65841 W. R. Grace and Co., published Dec. 23, 1999.
5. Coating Compositions
The wetting agents of the present invention can be used in coating compositions such as paints, rust treatments/inhibitors, undercoats, lacquers, varnishes and the like. The wetting agents may, for example, be used to suspend or aid in suspension of some or all of the components of the compositions, aid in even application or distribution of the components on a surface, increase the speed of drying or make drying uniform or more even. The composition may be water or oil based and they may be applied to a surface via brush, roller, aerosol, spray booth, or similar electrostatic spray means.
By coating compositions it is meant a variety of composition for application to a surface to coat the surface, such as paints, inks, primers, sealants, adhesives and the like. The coating composition may be applied to a variety of surfaces. For example, suitable surfaces include wood, metal, glass, plastic, laminates, cement and the like.
Typical adjunct ingredients found in coating compositions include, but are not limited to, monomers, fillers, pigments, solvents, dyes, flame retardants, cross-linking agents, preservatives, pigments, catalysts, co-catalysts, anti-foaming agents, resins, viscosity control agents, wetting agents other than those of the present invention, polymers, anti-oxidants, UV absorbers, conditioning agents, biocides, fungicides, light stabilizers, anti-oxidants, reducing agents, corrosion inhibitors, carriers, rheology modifiers, propellants, plasticizers, buffers, initiators, chain transfer agents, wood preservatives, and mixtures thereof. See U.S. Pat. No. 5,389,300 Schmitt et al., issued Feb. 14, 1995; U.S. Pat. No. 5,348,993 Daeumer et al., issued Sep. 20, 1994; U.S. Pat. No. 5,922,796 Colombet et al, issued Jul. 13, 1999; U.S. Pat. No. 5,157,069 Campbell issued Oct. 20, 1992; U.S. Pat. No. 4,265,797 Suk issued May 5, 1981, U.S. Pat. No. 6,060,556 Collins et al., issued May 9, 2000; U.S. Pat. No. 5,601,879 Anchor et al., issued Feb. 11, 1997; U.S. Pat. No. 5,681,880 Desor et al., issued Oct. 28, 1997; U.S. Pat. No. 5,880,190 Laura issued Mar. 9, 1999; U.S. Pat. No. 4,639,475 Dierichs et al., issued Jan. 27, 1987; U.S. Pat. No. 4,765,243 Schiefer et al., issued Aug. 23, 1988; WO 99/10464 Amway, published Mar. 4, 1999; WO 99/09104 Eastman Chemical Company, published February 1999; and WO 00/18484 Ashland Inc., published Apr. 6, 2000,
6. Fertilizers
The wetting agents of the present invention may be used in fertilizer compositions. By fertilizer compositions it is meant compositions that provide nutrients, food or the like to plants or that are designed to increase resistance to some pest or disease. They may be in the form of tablets, granules, powders, liquids, pastes, emulsions, suspensions, concentrates and the like.
Typical adjunct ingredients found in fertilizer compositions include, but are not limited to, trace elements, binders, wetting agents other than the wetting agents of the present invention, filler, thickener, preservative, blood and bone products, ammonium nitrates, lime, sand, sources of nitrogen, buffers, nitrification inhibitors, growth hormones, antibiotics, soil-improving components, humus, peat, potassium, phosphorous, solvent, carrier, defoaming agents, micronutrients, and mixtures thereof. See U.S. Pat. No. 5,482,529 Ahlnas et al., issued Jan. 9, 1996; U.S. Pat. No. 4,345,931 Meyer issued Aug. 24, 1982; U.S. Pat. No. 4,055,974 Jackson issued Nov. 1, 1997; and WO 98/39237 published Sep. 11, 1998.
7. Pharmaceuticals
The wetting agents of the present invention may be used in pharmaceutical compositions. They may be used to improve the dissolution of a medicament, such as in an oral suspension, enema or suppository, or may be used in the preparation of the pharmaceutical composition. The pharmaceutical compositions may be in any conventional form, such as suspension, powder, granule, tablet, capsule, caplet, suppository, lotion, cream, aerosols, emulsions, microemulsions, vapor, inhalant, liquid (such as those taken orally, nasally or through any other mucus membrane, subcutaneously or intramuscularly), adhesive patch and the like.
Typical adjunct ingredients found in pharmaceutical compositions include, but are not limited to, medicaments, fillers, lubricants, coating agents, buffers, adhesives, gelling agents, mould release agents, flavorings, sweeteners, carriers, stabilizers, humectants, coloring agents, extenders, preservatives, wetting agents other that the wetting agents of the present invention, solvent, electrolytes, and mixtures thereof. See U.S. Pat. No. 5,646,109 Owen et al., issued Jul. 8, 1997, U.S. Pat. No. 5,626,879 Anaebonam et al, issued May 6, 1997, and U.S. Pat. No. 5,897,548 Sacco et al, issued Apr. 27, 1999 and WO 94/07472 Pfizer, published Apr. 14, 1994.
8. Toothpastes
The wetting agents of the present invention may also be used in toothpastes, and/or associated oral hygiene products, such as dental rinses, moth washes, or in any other composition/product/process associated with dental hygiene that would be used at home or by a dental surgeon/technician, such as a fluoride gel. The wetting agents may be used, for example, in the processing/preparation of toothpaste, or to aid in suspension of one or more of the components of the tooth paste and/or improve mouth feel and foam quality during use.
Typical adjunct ingredients found in toothpastes include, but are not limited to, medicaments, dentifrices, abrasives, sources of fluorine, fillers, lubricants, coating agents, buffers, adhesives, gelling agents, polishing agents, antibacterial agents, flavorings, sweeteners, carriers, solvents, stabilizers, opacifying agents, coloring agents, extenders, preservatives, polymers, anti-calculus agents, dyes, iridescent particles, essential oil, wetting agents other that the wetting agents of the present invention, defoamers, solvent, humectants, electrolytes, binders, thickeners, rheology modifiers, and mixtures thereof. See U.S. Pat. No. 5,723,105 Viscio et al., issued Mar. 3, 1998, and WO 98/55084, Block Drug Company, published Dec. 10, 1998.
9. Metal Cleaners
The wetting agents of the present invention may also be used in metal cleaning compositions. The term xe2x80x9cmetal cleaningxe2x80x9d compositions is meant to include not only compositions which are used for degreasing metal surfaces, but also to include compositions which are used in cleaning electronic/electric components, such as those compositions used in clean rooms, metal cutting fluids, and the like. The compositions may be of any conventional form, such as liquid, emulsion, microemulsion, azeotrope, azeotrope like, and the like.
Typical adjunct ingredients found in metal cleaning compositions include, but are not limited to, abrasives, coating agents, buffers, gelling agents, polishing agents, carriers, solvents, stabilizers, coloring agents, polymers, wetting agents other that the wetting agents of the present invention, defoamers, electrolytes, thickeners, rheology modifiers, and mixtures thereof. See U.S. Pat. No. 4,091,826 Bahrke issued May 30, 1978; U.S. Pat. No. 4,778,532 McConnell et al., issued Oct. 18, 1998; U.S. Pat. No. 5,503,681 Inada et al., issued Apr. 2, 1996; U.S. Pat. No. 5,628,833 McCormack et al. issued May 13, 1997; and EP Patent Application No. 971000 to Tokyo Electron Limited, published Jan. 12, 2000.
10. Paper Processing
The wetting agent of the present invention may also be used in both the processes for preparing paper as well as treatment of waste material produced during these processes. The wetting agents of the present invention may be used during the preparation of paper, for example, to increase the tactile softness of the paper, or to improve the wetting and or dispersion of the components as needed. Additionally, the wetting agents of the present invention may be used to control the foam generation in any liquids used in the paper making process, especially foaming any waste liquids, such as black liquor. See WO 97/35067 Betzdearbom Inc, published Sep. 25, 1997.
The present invention also provides for a method of adding a wetting agent according to the present invention to a liquid or composition associated with a papermaking process to reduce, control or eliminate any foam produced by the liquid or composition. See WO 97/35067 Betzdearbom Inc, published Sep. 25, 1997, WO 94/05856 published Mar. 17, 1994 and U.S. Pat. No. 5,660,684 Li et al., issued Aug. 26, 1997.
11. Drilling Fluids
The wetting agents of the present invention may also be used in drilling fluids, or so-called drilling muds. A drilling fluid may be circulated down through the drill pipe, out the drill bit and back up to the surface through the annulus between the drill pipe and the borehole wall. The drilling fluid has a number of purposes, including cooling and lubricating the bit, carrying the cuttings from the hole to the surface and exerting hydrostatic pressure against the borehole wall to prevent the flow of fluids from the surrounding formation into the borehole.
A drilling fluid with relatively high viscosity at high shear rates can place undesirable mechanical constraints on the drilling equipment and may even damage the reservoir. Higher viscosity fluids also exert higher pressures outward on the borehole, which may cause mechanical damage to the formation and reduce the ability of the well to produce oil and/or gas. Higher viscosity fluids may also fracture the formation, requiring a drilling shutdown in order to seal any fractures. Damage to a reservoir is particularly harmful if it occurs while drilling through the xe2x80x9cpayzonexe2x80x9d, or the zone believed to hold recoverable oil or gas. In order to avoid such damage, a different fluid, known as a xe2x80x9cdrill-inxe2x80x9d fluid, is pumped through the drill pipe while drilling in the pay zone.
Another type of fluid used in oil and gas wells is a xe2x80x9ccompletion fluidxe2x80x9d. A completion fluid is pumped down a well after drilling operations are completed during the xe2x80x9ccompletion phasexe2x80x9d. Drilling mud is typically removed from the well using xe2x80x9ccompletion fluidxe2x80x9d. Then, the equipment required to produce fluids, oil or gas, to the surface is installed in the well.
The wetting agents of the present invention are suitable for use in all types of drilling fluids, such as drilling muds, xe2x80x9cdrill-inxe2x80x9d fluids and xe2x80x9ccompletionxe2x80x9d fluids.
Typical adjunct ingredients found in drilling fluids include, but are not limited to, defoamers, solvent, wetting agents other than the wetting agents of the present invention, corrosion inhibitors, polymers, brine, viscosity agents, rehology agents, water soluble polymers, drilled solids, clay, weighting materials, gelling agents, fluid loss additives, and mixtures thereof. See U.S. Pat. No. 5,300,542 Gopalkrishan issued Apr. 5, 1994, WO 98/42795 published Oct. 1, 1998 and 00/26321 published May 11, 2000.
12. Miscellaneous
The wetting agents of the present invention may also be used in a variety of compositions or applications. Examples of these include, but are not limited to:
Lens Cleaners
The wetting agents may be used in composition and/or methods for cleaning lenses, such as spectacles, contact lenses (including hard lenses, rigid gas permeable and soft type lenses) and the like. Adjuncts that may be used in these compositions include, but are not limited to, solvents, buffer, abrasives, enzymes, enzyme inhibitors, anti-bacterial agents, germicides, preservatives, humectants, wetting agents other than the wetting agent of the present invention, tonicity agents, viscosity builders, and mixtures thereof. See WO 99/43363 Bausch and Lomb Inc, published Sep. 2, 1999.
Furthermore, these wetting agents of the present invention may also be used in the compositions and/or processes for the manufacture or polishing of lenses. See U.S. Pat. No. 4,546,123 Schafer et al., issued Oct. 8, 1985.
Other Applications
The wetting agent of the present invention may be used in leather care compositions, see U.S. Pat. No. 4,554,083 Soldanski et al., issued Nov. 19, 1985; compositions for the suppression of dust or in ore flotation, see U.S. Pat. No. 5,412,007 Hendrix et al., issued May 2, 1995 and U.S. Pat. No. 4,746,543 Zikan et al., issued May 24, 1988; compositions for printers and photocopies, such as ink jet compositions, see U.S. Pat. No. 4,680,332 Hair et al., issued Jul. 14, 1987; in foods, see U.S. Pat. No. 4,752,485 Sharma et al., issued Jun. 21, 1998; in explosives, especially in oil-in-water emulsion explosives, see U.S. Pat. No. 4,784,706 McKenzie issued Nov. 15, 1988; in photography, especially in photographic emulsions, see U.S. Pat. No. 5,215,873 Kiesslich et al., issued Jun. 1, 1993; emulsification of silicones, see U.S. Pat. No. 5,338,352 Breneman et al., issued Aug. 16, 1994; in dyes or dying compositions/solutions, see U.S. Pat. No. 5,360,457 Ruggiero et al, issued Nov. 1, 1994; in catalysts, and in their manufacture and preparation, see U.S. Pat. No.5,958,819 Johnson et al., issued Sep. 28, 1999; in ice melting and defogging compositions, see U.S. Pat. No. 6,039,890 Ossian et al., issued Mar. 21, 2000; and in the preparation and manufacture of diaphragms for electrolytic cells, see U.S. Pat. No. 6,059,944 Dubois et al., issued May 9, 2000.
It is to be understood that the above illustrative compositions, methods and processes are to be in no way construed as limiting of the scope of the present invention. They are merely illustrative of some and not all of the possible uses the wetting agents of the present invention.
All documents cited are in relevant part, incorporated herein by reference.
The following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified.